EP3083874B1 - Use of a copolymer made from styrene sulphonic acid to inhibit or slow the formation of sulphide deposits - Google Patents

Use of a copolymer made from styrene sulphonic acid to inhibit or slow the formation of sulphide deposits Download PDF

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EP3083874B1
EP3083874B1 EP14830835.6A EP14830835A EP3083874B1 EP 3083874 B1 EP3083874 B1 EP 3083874B1 EP 14830835 A EP14830835 A EP 14830835A EP 3083874 B1 EP3083874 B1 EP 3083874B1
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unit
poly
solution
carboxylic acid
copolymer
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German (de)
French (fr)
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EP3083874A1 (en
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Christian Hurtevent
Salima BARAKA-LOKMANE
John-Richard ORDONEZ-VARELA
Olivier Tillement
Fabien ROSSETTI
Mahmoud OULD METIDJI
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Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
TotalEnergies Onetech SAS
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Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
TotalEnergies Onetech SAS
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
    • C09K8/532—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/30—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/30—Sulfur
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B37/00—Methods or apparatus for cleaning boreholes or wells
    • E21B37/06—Methods or apparatus for cleaning boreholes or wells using chemical means for preventing, limiting or eliminating the deposition of paraffins or like substances

Definitions

  • the present invention relates to the use of a copolymer containing (i) a unit comprising an optionally neutralized styrene sulfonic acid unit and (ii) a unit containing an optionally neutralized (poly)carboxylic acid unit and/or a (poly )amido-amine, to inhibit or slow down the formation of sulphide deposits during the extraction of gas or oil. It also relates to a method for inhibiting or slowing down the formation of sulphide deposits during the extraction of gas or oil, comprising the injection, into a wellbore, an underground formation or an oil or gas well, of a fluid containing the aforementioned copolymer.
  • Oil production fluids consist of oil, gas and water.
  • Reservoir waters can be very salty waters that contain many elements.
  • the produced waters may contain elements such as iron, zinc or lead, originating from the rocks with which the reservoir waters have been in contact for millions of years.
  • the gas associated with the production contains sulphides such as hydrogen sulphide, then sulphides of iron, zinc and/or lead can be formed.
  • These salts can settle in the immediate vicinity tank or in the production facilities such as the pipes ("tubing").
  • Such deposits have in particular been observed during the concomitant production of gas and brine in the Gulf of Mexico and in the British sector of the North Sea. To eliminate them, it is necessary to regularly clean the equipment, which negatively affects the productivity of the process.
  • sulphide deposit inhibitor a particular copolymer such as a styrene sulphonic acid/maleic anhydride copolymer. It has already been suggested to use such a copolymer as an inhibitor of non-sulphide inorganic deposits, based on calcium carbonate and barium sulphate, in oil wells ( FR 2 803 304 ). These deposits are generally formed when the brine present in the reservoir comes into contact with the fluid injected to recover the oil. It is commonly accepted that calcium carbonate or sulphate scale inhibitors are not suitable for preventing the formation of sulphide deposits.
  • the present invention relates to the use of a copolymer containing (i) a unit comprising an optionally neutralized styrene sulfonic acid unit and (ii) a unit containing an optionally neutralized (poly)carboxylic acid unit and/or a (poly ) amido-amine, for inhibiting or slowing down the formation of sulphide deposits, in particular sulphides of lead, iron and/or zinc, during the extraction of gas or oil.
  • It also relates to a method for inhibiting or slowing down the formation of sulphide deposits, in particular lead, iron and/or zinc sulphides, during the extraction of gas or oil, comprising the injection, into a well drilling site, an underground formation or an oil or gas well, of a fluid containing a copolymer comprising (i) a unit comprising an optionally neutralized styrene sulphonic acid unit and (ii) a unit comprising a optionally neutralized (poly)carboxylic acid unit and/or a (poly)amido-amine unit.
  • a copolymer comprising (i) a unit comprising an optionally neutralized styrene sulphonic acid unit and (ii) a unit comprising a optionally neutralized (poly)carboxylic acid unit and/or a (poly)amido-amine unit.
  • the inventors have put forward the hypothesis that the inhibitory effect of the copolymers according to the invention was based on a preferential complexation of the surface sites of the zinc and lead sulphide particles by the acid functions carboxylic acid or amido-amine of these copolymers and on the steric repulsion generated by the sulphonic acid functions, these two actions contributing to slow the growth of the crystals of sulphide formed and therefore the kinetics of formation of the precipitates of sulphide of lead, iron and zinc. In practice, these precipitates therefore do not have time to form under the operating conditions of a gas or oil field, since exceeding the saturation threshold remains limited in time in this type of process.
  • the copolymers according to the invention can also exercise their known function of inhibiting the formation of calcium carbonate or barium sulphate deposits, in particular.
  • the copolymer used according to the present invention may consist solely of (i) units comprising (and preferably consisting of) an optionally neutralized styrene sulfonic acid unit and (ii) units containing (and preferably consisting of) an acid unit optionally neutralized (poly)carboxylic acid and/or at least one (poly)amido-amine unit.
  • (poly)carboxylic acid unit is meant a unit carrying one or several carboxylic acid functions.
  • This unit is advantageously obtained from an unsaturated monomer carrying at least one, and preferably two, carboxylic acid functions, chosen for example from maleic acid, fumaric acid, itaconic acid, citraconic acid, cis-1,2,3,6-tetrahydro-phthalic anhydride, maleic acid being preferred.
  • carboxylic acid units can be neutralized using sodium, potassium or ammonium salts, preferably sodium salts.
  • the (poly)amido-amine unit can be obtained by reaction of all or part of the carboxylic acid functions with a compound, preferably a polymer, carrying at least two primary or secondary amine functions, which can be chosen in particular from: polyamines such as as DETA (diethylene triamine), TETA (triethylene tetramine), TEPA (tetraethylene pentamine), dihexylene triamine and polyethyleneimine (PEI); silicone polymers, in particular polydimethylsiloxanes, functionalized with amino groups; chitosans; polypeptides and proteins, preferably DETA and PEI.
  • DETA diethylene triamine
  • TETA triethylene tetramine
  • TEPA tetraethylene pentamine
  • PEI polyethyleneimine
  • silicone polymers in particular polydimethylsiloxanes, functionalized with amino groups
  • chitosans polypeptides and proteins, preferably DETA and PEI.
  • the molar percentage, in the copolymer according to the invention, of units containing an optionally neutralized styrene sulfonic acid unit be between 10 and 90%, preferably between 25 and 75% and, better still, between 50 and 70% .
  • This copolymer may contain at least one other unit chemically distinct from those mentioned above and which may for example represent at most 20 mol% and preferably at most 10 mol%, relative to the number of total moles of monomer units in said copolymer.
  • This other unit can be chosen in particular from (meth)acrylamides, (meth)acrylic acid esters, vinyl acetate, styrene and vinyltoluene.
  • all or part of the carboxylic acid functions of the copolymer are substituted by amido-amine functions resulting, as indicated previously, from the reaction of these carboxylic acid functions with at least two amine functions primary or secondary carried by a compound which is reacted with the units containing at least one (poly)carboxylic acid unit of the copolymer according to the invention. It has in fact been observed that these copolymers exhibit improved properties for inhibiting the formation of sulphide deposits.
  • copolymers make it possible to obtain a prolonged inhibitory effect, by progressive hydrolysis of the amide functions, and also more effective, insofar as the free doublet of the nitrogen atom of the amine functions not having participated in the bonds amides is useful for complexing the surface sites of zinc and lead sulfide particles.
  • These copolymers with amido-amine functions also limit the interactions between the (poly)carboxylic acid units and deposits of barium sulphate or calcium carbonate, for example, which can make it possible to prevent the copolymer from reacting exclusively with these deposits which tend, under certain conditions , to form before the sulphide deposits.
  • the copolymer used according to the invention generally has an average molecular weight of between 10 and 50 kDa.
  • This copolymer can be obtained according to conventional processes of radical polymerization in aqueous or aqueous-alcoholic way and at acid pH. It is also commercially available from ALDRICH or AKZO NOBEL.
  • the polymer according to the invention can be used in particular in oil wells operating at high pressure, that is to say at more than 10 MPa, for example from 20 to 150 MPa, and at high temperature, that is to say from 150 to 250°C, for example from 200 to 230°C.
  • This polymer can be injected into the well as an additive in a drilling fluid.
  • This drilling fluid may contain from 1 to 10 ppm of the polymer described above.
  • the polymer described above can be injected into the well in "squeeze", that is to say following a process consisting in rinsing the well with sea water, then injecting a fluid containing this polymer into the well and again introducing sea water into the well to disperse the polymer in the reservoir and allow it to adsorb on the underground rock formations.
  • the injected fluid may contain about 10% by weight of the polymer described above.
  • the fluid carrying the copolymer according to the invention may also contain other additives such as corrosion inhibitors, paraffin inhibitors, surfactants or demulsifying agents, dispersing agents, in particular dispersants of asphaltene, foaming agents or anti-foaming agents, biocidal agents, oxygen scavengers, chelating agents such as EDTA and DTPA, and mixtures thereof.
  • additives such as corrosion inhibitors, paraffin inhibitors, surfactants or demulsifying agents, dispersing agents, in particular dispersants of asphaltene, foaming agents or anti-foaming agents, biocidal agents, oxygen scavengers, chelating agents such as EDTA and DTPA, and mixtures thereof.
  • this fluid also contains at least one polymer bearing amine functions, such as the polyamines mentioned above, in particular DETA or PEI, silicone polymers bearing amine functions, and their mixtures.
  • polymer bearing amine functions such as the polyamines mentioned above, in particular DETA or PEI, silicone polymers bearing amine functions, and their mixtures.
  • Example 1 Preparation of an inhibitor solution of poly(sodium 4-styrenesulfonate)
  • the polymer purchased from Sigma Aldrich ( CAS: 25704-18-1 ; (C 8 H 7 NaO 3 S) n ), has a molar mass of the order of 100 kDa.
  • Ten grams of poly(sodium 4-styrenesulfonate) are weighed into a 100 mL bottle. The mass is then adjusted to 100 grams by adding ultrapure water. pH is then about 8.7. The pH is then adjusted to 4.5 by adding 6M hydrochloric acid.
  • Example 2 Preparation of an inhibitor solution of sodium salt of poly (4-styrenesulfonic acid-co-maleic acid) (or F11)
  • the polymer has a ratio of three styrene sulfonic acid functions for one maleic acid function.
  • Ten grams of Fil are weighed into a 100 mL bottle. The mass is then adjusted to 100 grams by adding ultrapure water. The pH of around 7.5 is adjusted to 4.5 by adding 6M hydrochloric acid.
  • Example 3 Preparation of an inhibitor solution of sodium salt of poly (4-styrenesulfonic acid-co-maleic acid) (or Fllb)
  • the polymer has an equimolar ratio of styrene sulfonic acid and maleic acid functions.
  • Ten grams of Fl1b are weighed into a 100 mL bottle. The mass is then adjusted to 100 grams by adding ultrapure water. The pH of about 7.5 is adjusted to 4.5 by adding 6M hydrochloric acid.
  • pressure variations are studied as a function of time.
  • An increase in pressure in fact reflects a gas release linked to a probable decomposition of the product.
  • the change in appearance of the solutions can also provide information on the stability of the products tested.
  • a pH measurement can be performed before and after ageing.
  • An analysis of the products by GPC before and after aging can also highlight the stability of the products.
  • a sulfur solution is prepared at two concentrations (100 mg.L -1 and 200 mg.L -1 ) of sulfur by dilution of Na 2 S.9H 2 O (Aldrich, 98 wt%) in ultra pure water.
  • the contents of the vial are poured into an Erlenmeyer flask equipped with a serum cap through which a pH meter continuously measures the pH of the solution.
  • the whole is placed under mechanical agitation.
  • Additions of 0.12M HCl solution are made using a syringe via the serum cap in order to reach a pH of 5.5.
  • the solution is then distributed using a syringe into sealed 15 mL bottles fitted with serum caps. Samples are stored for a maximum of one week at 5°C.
  • a zinc solution is prepared at 150 mg.L -1 of zinc by dissolving 157 mg of ZnCl 2 (Aldrich, 98wt%) in a 500 mL volumetric flask using a saline solution (25 gL -1 [ Na + ] and 5 gL -1 [Ca 2+ ]). The pH of the solution is adjusted to 4.5 by successive additions of a 0.12M HCl solution.
  • the inhibitors are prepared at 5% by weight in water and the pH is adjusted to 4.5 using a 0.12M and 12M HCl solution. The inhibitors are then added at different concentrations (10, 30, 50 and 100 ppm) in the zinc solution prepared previously. The pHs are checked and readjusted if necessary using 0.12M HCl or 0.1M NaOH.
  • the measurements are carried out using a Varian Cary Eclipse spectrofluorimeter.
  • the fluorescence of ZnS is first of all evaluated by analysis of a control sample in which Zinc is placed in the presence of sulfur without particular saline conditions.
  • Variations in the sulfur concentration over time, linked to the release of hydrogen sulphide, make it necessary to change the capsule every half-dozen measurements, as well as to make frequent references between measurements.
  • the analyzes are carried out first of all at ambient temperature (20°C) then at 80°C. They are made in PMMA tanks.
  • F11-DETA solution of Example 4 Five milliliters of the F11-DETA solution of Example 4 are placed in a 10 mL bottle to which 5 mL of ultrapure water are added. A 5% by weight solution of F11-DETA (10:2) is then obtained. The pH of this solution is adjusted to 4.5 by adding 6M HCl. After which, 1, 4 and 10 ⁇ L of this solution are placed using a micropipette in 10mL bottles. 9999, 9996 and 9990 ⁇ L of the zinc solution described above are then added respectively to each flask to obtain three solutions at 5, 20 and 50 ppm of Fl1-DETA. The pH of the solutions is adjusted to 4.5 if necessary by adding 0.12M HCl.
  • Two saline solutions containing metal cations (A) and sulfur (B) are mixed and then passed through a tube where a deposit forms.
  • the tube is equipped with a filter.
  • the inhibitors are mixed in solution A and are tested between 5 and 30 ppm.
  • An analysis of the filter by SEM then by EDX makes it possible to obtain precise information on the quantity and nature of the deposits formed.
  • the solutions containing the PSS used are based on solution A3 of Table 1, to which are added quantities of the PSS solution of example 1.
  • the solutions then obtained are at 30, 50 and 100 ppm PSS. They are o-injected with solution B from Table 1, via an alloy tube (Ni 72 Cr 16 Fr 8 ) 1 mm outside diameter and 0.8 mm inside diameter. The two solutions then pass through a 7 ⁇ m filter. The solutions are injected with a flow rate of 10 mL/min. A differential pressure measurement is made between the inlet and the outlet of the filter. The tests are carried out at 125°C and under a pressure of 45 bar. The results obtained are collated in Table 2 below.
  • the solutions containing the Fl1 used are based on the solution A2 of Table 1, to which are added quantities of the solution of Fl1 of example 2.
  • the solutions obtained are at 5, 10, 30 and 100 ppm. They are co-injected with solution B of Table 1, via an alloy tube (Ni 72 Cr 16 Fr 8 ) with an outside diameter of 1 mm and an inside diameter of 0.8 mm. The two solutions then pass through a 7 ⁇ m filter. The solutions are injected with a flow rate of 10mL/min. A differential pressure measurement is made between the inlet and the outlet of the filter. The tests are carried out at 125°C and under a pressure of 45 bar. The results are collated in Table 3 below.
  • Fl1 is active from 5 ppm. Indeed, from this concentration, Fl1 slows the growth of ZnS.
  • the solutions containing Fl1-DETA used are based on solution A2 of Table 1, to which are added given quantities of the solution of Fl1-DETA of example 4.
  • the solutions obtained are at 1, 3, 5, 10 and 30 ppm of Fl1-DETA. They are co-injected with solution B of Table 1, via an alloy tube (Ni 72 Cr 16 Fr 8 ) with an outside diameter of 1 mm and an inside diameter of 0.8 mm. The two solutions then pass through a 7 ⁇ m filter. The solutions are injected with a flow rate of 10 mL/min. A differential pressure measurement is made between the inlet and the outlet of the filter. The tests are carried out at 125°C and under a pressure of 45 bar. The results obtained are collated in Table 4 below.
  • Fl1-DETA is active from 3 ppm. Indeed, from this concentration, no increase in pressure is observed, which reflects the absence of formation of ZnS deposit.

Description

DOMAINE TECHNIQUETECHNICAL AREA

La présente invention se rapporte à l'utilisation d'un copolymère renfermant (i) une unité comprenant un motif acide styrène sulfonique éventuellement neutralisé et (ii) une unité renfermant un motif acide (poly)carboxylique éventuellement neutralisé et/ou un motif (poly)amido-amine, pour inhiber ou ralentir la formation de dépôts sulfures lors de l'extraction de gaz ou de pétrole. Elle se rapporte également à une méthode pour inhiber ou ralentir la formation de dépôts sulfures lors de l'extraction de gaz ou de pétrole, comprenant l'injection, dans un puits de forage, une formation souterraine ou un puits de pétrole ou de gaz, d'un fluide renfermant le copolymère précité.The present invention relates to the use of a copolymer containing (i) a unit comprising an optionally neutralized styrene sulfonic acid unit and (ii) a unit containing an optionally neutralized (poly)carboxylic acid unit and/or a (poly )amido-amine, to inhibit or slow down the formation of sulphide deposits during the extraction of gas or oil. It also relates to a method for inhibiting or slowing down the formation of sulphide deposits during the extraction of gas or oil, comprising the injection, into a wellbore, an underground formation or an oil or gas well, of a fluid containing the aforementioned copolymer.

ARRIERE-PLAN DE L'INVENTIONBACKGROUND OF THE INVENTION

Les fluides de production pétrolière sont constitués de pétrole, de gaz et d'eau. Les eaux de réservoir peuvent être des eaux très salées qui contiennent de nombreux éléments. En particulier, à haute température, les eaux de production peuvent contenir des éléments comme le fer, le zinc ou le plomb, provenant des roches avec lesquelles les eaux de réservoir ont été en contact pendant des millions d'années. Quand le gaz associé à la production contient des sulfures comme le sulfure d'hydrogène, on peut alors former des sulfures de fer, de zinc et/ou de plomb. Ces sels peuvent se déposer à proximité immédiate du réservoir ou dans les installations de production comme les tuyauteries ("tubing"). De tels dépôts ont en particulier été observés lors de la production concomitante de gaz et de saumure dans le Golfe du Mexique et dans le secteur britannique de la Mer du Nord. Pour les éliminer, il est nécessaire de nettoyer régulièrement les équipements, ce qui affecte négativement la productivité du procédé.Oil production fluids consist of oil, gas and water. Reservoir waters can be very salty waters that contain many elements. In particular, at high temperatures, the produced waters may contain elements such as iron, zinc or lead, originating from the rocks with which the reservoir waters have been in contact for millions of years. When the gas associated with the production contains sulphides such as hydrogen sulphide, then sulphides of iron, zinc and/or lead can be formed. These salts can settle in the immediate vicinity tank or in the production facilities such as the pipes ("tubing"). Such deposits have in particular been observed during the concomitant production of gas and brine in the Gulf of Mexico and in the British sector of the North Sea. To eliminate them, it is necessary to regularly clean the equipment, which negatively affects the productivity of the process.

Une solution pour éliminer ces dépôts a consisté à effectuer des lavages acides. Outre leur courte durée d'action, ces traitements ne sont toutefois pas sans risques pour l'homme et les équipements, en particulier dans des conditions de haute pression et haute température.One solution to remove these deposits has been to perform acid washes. In addition to their short duration of action, these treatments are however not without risks for humans and equipment, in particular under conditions of high pressure and high temperature.

Pour remédier à ce problème, il est possible d'inhiber la formation de ces dépôts par injection d'inhibiteurs en continu, en fond de puits, quand des installations sont en place. Dans le cas contraire, l'injection du produit se fait par une technique d'injection appelée « squeeze ». Cette technique consiste à injecter une grande quantité de produit dans le réservoir pétrolier alors que la production est arrêtée. L'inhibiteur de dépôt injecté dans le réservoir doit s'adsorber sur la roche pendant l'injection et être relargué progressivement lors de la remise en production, afin d'empêcher la formation des dépôts sur une longue période de temps, pendant la production de l'eau de réservoir.To remedy this problem, it is possible to inhibit the formation of these deposits by injecting inhibitors continuously, downhole, when installations are in place. Otherwise, the injection of the product is done by an injection technique called “squeeze”. This technique consists of injecting a large quantity of product into the oil reservoir while production is stopped. The scale inhibitor injected into the reservoir must adsorb onto the rock during injection and be gradually released when restarted, in order to prevent the formation of deposits over a long period of time, during the production of tank water.

Parmi les solutions proposées dans l'art antérieur pour inhiber la formation de dépôts de sulfures, il a été suggéré d'ajouter au fluide de forage injecté dans le puits un agent inhibiteur capable de prévenir la formation des cristaux de sulfures, d'empêcher leur croissance ou de les disperser. Ainsi, un polymère de faible poids moléculaire, qui est un homo- ou copolymère de vinyl sulfonate, a été étudié par M.M. JORDAN et al. dans le document SPE 64427 présenté à la Conférence SPE Asie Pacifique à Brisbane (Australie), le 16 octobre 2000 . D'autres inhibiteurs ont été proposés dans les documents US-7,159,655 et US-7,398,824 . Il s'agit respectivement de copolymères d'acrylamide, d'ammonium quaternaire et éventuellement d'acrylate, et de copolymères d'acrylamide, de sel de diallyldiméthylammonium et éventuellement d'acrylate, qui sont introduits dans un fluide porteur ou dans de la saumure. Il est indiqué que ces polymères sont plus solubles, dans les saumures de haute densité, que des polymères à base d'acide acrylamidométhylpropane sulfonique, d'acide maléique et d'acide acrylique. Le document GB-2 448 442 rapporte l'introduction du même type de polymère dans un fluide de fracturation. Le document US-5,171,459 suggère, de son côté, l'utilisation d'alkyldiphényléther sulfonates tels que le produit Dowfax de DOW CHEMICAL. Il est démontré que ces composés dispersent mieux les dépôts de sulfures que d'autres polymères sulfonés tels qu'un poly(vinyl sulfonate) et un copolymère vinylsulfonate / styrène / anhydride maléique. Le document US2009/0143252 décrit une méthode pour prévenir la formation des dépôts sulfures comprenant une étape de traitement d'un fluide de production avec un additif comprenant un homopolymère d'un monomère acrylamide spécifique.Among the solutions proposed in the prior art to inhibit the formation of sulphide deposits, it has been suggested to add to the drilling fluid injected into the well an inhibiting agent capable of preventing the formation of sulphide crystals, of preventing their growth or of dispersing them. Thus, a low molecular weight polymer, which is a vinyl sulfonate homo- or copolymer, was studied by MM JORDAN et al. in document SPE 64427 presented at the SPE Asia Pacific Conference in Brisbane, Australia, October 16, 2000 . Other inhibitors have been proposed in the papers US-7,159,655 and US-7,398,824 . These are respectively copolymers of acrylamide, quaternary ammonium and optionally acrylate, and copolymers of acrylamide, diallyldimethylammonium salt and optionally acrylate, which are introduced into a carrier fluid or into brine . These polymers are said to be more soluble in high density brines than polymers based on acrylamidomethylpropane sulfonic acid, maleic acid and acrylic acid. The document GB-2 448 442 reports the introduction of the same type of polymer into a fracturing fluid. The document US-5,171,459 suggests, for its part, the use of alkyldiphenyl ether sulfonates such as the product Dowfax from DOW CHEMICAL. These compounds have been shown to disperse sulfide deposits better than other sulfonated polymers such as poly(vinyl sulfonate) and vinyl sulfonate/styrene/maleic anhydride copolymer. The document US2009/0143252 describes a method for preventing the formation of sulphide deposits comprising a step of treating a production fluid with an additive comprising a homopolymer of a specific acrylamide monomer.

Il a toutefois été observé que les inhibiteurs de dépôts de sulfures connus n'étaient pas efficaces pour une utilisation dans des conditions de haute pression et haute température. Il en est de même des phosphonates qui sont connus pour se dégrader à haute température, les produits de dégradation de ces composés présentant en outre une très faible solubilité en présence de cations alcalino-terreux, ce qui réduit fortement leur utilisation et la rend même quasi impossible dans des réservoir à plus de 150°C.However, it has been observed that known sulphide deposition inhibitors are not effective for a use under high pressure and high temperature conditions. The same applies to phosphonates which are known to degrade at high temperature, the degradation products of these compounds also having a very low solubility in the presence of alkaline-earth cations, which greatly reduces their use and even makes it almost not possible in tanks over 150°C.

Il subsiste donc le besoin de disposer d'un composé permettant d'inhiber ou de ralentir la formation de dépôts de sulfures, en particulier de sulfures de zinc, de fer et de plomb, qui soit stable à haute température et haute pression et qui puisse également être efficace contre la formation d'autres dépôts inorganiques ou compatible avec les inhibiteurs utilisés à cette fin. Il serait en outre souhaitable que ce composé puisse être libéré de manière prolongée.There therefore remains the need for a compound which makes it possible to inhibit or slow down the formation of sulphide deposits, in particular of sulphides of zinc, iron and lead, which is stable at high temperature and high pressure and which can also be effective against the formation of other inorganic deposits or compatible with inhibitors used for this purpose. It would also be desirable for this compound to be able to be released over a prolonged period.

Les inventeurs ont démontré que ces besoins pouvaient être satisfaits en utilisant, comme inhibiteur de dépôts de sulfures, un copolymère particulier tel qu'un copolymère acide styrène sulfonique / anhydride maléique. Il a déjà été suggéré d'utiliser un tel copolymère comme inhibiteur de dépôts inorganiques non sulfurés, à base de carbonate de calcium et de sulfate de baryum, dans les puits pétroliers ( FR 2 803 304 ). Ces dépôts sont généralement formés lors de la mise en contact de la saumure présente dans le réservoir avec le fluide injecté pour récupérer le pétrole. Il est communément admis que les inhibiteurs de dépôt de carbonate ou de sulfate de calcium ne sont pas adaptés pour empêcher la formation de dépôts de sulfures. Cela résulte du fait que les carbonate de calcium et sulfate de baryum portent des charges de surface positives, contrairement aux sulfures de plomb, de fer et de zinc dont le point isoélectrique est inférieur à 4 ( M. Kosmulski, Journal of Colloid and Interface Science, 35, (2011), 1-15 ). Les polymères anioniques utilisés pour inhiber la formation des premiers ne sont donc pas adaptés à développer des interactions électrostatiques avec les seconds. Ainsi, il n'était pas prévisible que les copolymères précités pouvaient offrir une solution aux besoins précités.The inventors have demonstrated that these needs could be satisfied by using, as sulphide deposit inhibitor, a particular copolymer such as a styrene sulphonic acid/maleic anhydride copolymer. It has already been suggested to use such a copolymer as an inhibitor of non-sulphide inorganic deposits, based on calcium carbonate and barium sulphate, in oil wells ( FR 2 803 304 ). These deposits are generally formed when the brine present in the reservoir comes into contact with the fluid injected to recover the oil. It is commonly accepted that calcium carbonate or sulphate scale inhibitors are not suitable for preventing the formation of sulphide deposits. This results from the fact that the calcium carbonate and barium sulphate carry positive surface charges, unlike lead, iron and zinc sulphides whose isoelectric point is less than 4 ( M. Kosmulski, Journal of Colloid and Interface Science, 35, (2011), 1-15 ). The anionic polymers used to inhibit the formation of the former are therefore not suitable for developing electrostatic interactions with the latter. Thus, it was not foreseeable that the aforementioned copolymers could offer a solution to the aforementioned needs.

RESUME DE L'INVENTIONSUMMARY OF THE INVENTION

La présente invention a pour objet l'utilisation d'un copolymère renfermant (i) une unité comprenant un motif acide styrène sulfonique éventuellement neutralisé et (ii) une unité renfermant un motif acide (poly)carboxylique éventuellement neutralisé et/ou un motif (poly)amido-amine, pour inhiber ou ralentir la formation de dépôts sulfures, notamment de sulfures de plomb, de fer et/ou de zinc, lors de l'extraction de gaz ou de pétrole.The present invention relates to the use of a copolymer containing (i) a unit comprising an optionally neutralized styrene sulfonic acid unit and (ii) a unit containing an optionally neutralized (poly)carboxylic acid unit and/or a (poly ) amido-amine, for inhibiting or slowing down the formation of sulphide deposits, in particular sulphides of lead, iron and/or zinc, during the extraction of gas or oil.

Elle a également pour objet une méthode pour inhiber ou ralentir la formation de dépôts sulfures, notamment de sulfures de plomb, de fer et/ou de zinc, lors de l'extraction de gaz ou de pétrole, comprenant l'injection, dans un puits de forage, une formation souterraine ou un puits de pétrole ou de gaz, d'un fluide contenant un copolymère renfermant (i) une unité comprenant un motif acide styrène sulfonique éventuellement neutralisé et (ii) une unité renfermant un motif acide (poly)carboxylique éventuellement neutralisé et/ou un motif (poly)amido-amine.It also relates to a method for inhibiting or slowing down the formation of sulphide deposits, in particular lead, iron and/or zinc sulphides, during the extraction of gas or oil, comprising the injection, into a well drilling site, an underground formation or an oil or gas well, of a fluid containing a copolymer comprising (i) a unit comprising an optionally neutralized styrene sulphonic acid unit and (ii) a unit comprising a optionally neutralized (poly)carboxylic acid unit and/or a (poly)amido-amine unit.

Sans vouloir être liés par cette théorie, les inventeurs ont émis l'hypothèse selon laquelle l'effet inhibiteur des copolymères selon l'invention était basé sur une complexation préférentielle des sites de surface des particules de sulfure de zinc et de plomb par les fonctions acide carboxylique ou amido-amine de ces copolymères et sur la répulsion stérique engendrée par les fonctions acide sulfonique, ces deux actions contribuant à ralentir la croissance des cristaux de sulfure formés et donc la cinétique de formation des précipités de sulfure de plomb, de fer et de zinc. En pratique, ces précipités n'ont donc pas le temps de se former dans les conditions d'exploitation d'un gisement de gaz ou de pétrole, puisque le dépassement du seuil de saturation reste limité dans le temps dans ce type de procédé. Les copolymères selon l'invention peuvent en outre exercer leur fonction connue d'inhibition de la formation de dépôts de carbonate de calcium ou de sulfate de baryum, notamment.Without wishing to be bound by this theory, the inventors have put forward the hypothesis that the inhibitory effect of the copolymers according to the invention was based on a preferential complexation of the surface sites of the zinc and lead sulphide particles by the acid functions carboxylic acid or amido-amine of these copolymers and on the steric repulsion generated by the sulphonic acid functions, these two actions contributing to slow the growth of the crystals of sulphide formed and therefore the kinetics of formation of the precipitates of sulphide of lead, iron and zinc. In practice, these precipitates therefore do not have time to form under the operating conditions of a gas or oil field, since exceeding the saturation threshold remains limited in time in this type of process. The copolymers according to the invention can also exercise their known function of inhibiting the formation of calcium carbonate or barium sulphate deposits, in particular.

DESCRIPTION DETAILLEE DE MODES DE REALISATIONDETAILED DESCRIPTION OF EMBODIMENTS

Le copolymère utilisé selon la présente invention peut être constitué uniquement (i) d'unités comprenant (et de préférence constituées par) un motif acide styrène sulfonique éventuellement neutralisé et (ii) d'unités renfermant (et de préférence constituées par) un motif acide (poly)carboxylique éventuellement neutralisé et/ou au moins un motif (poly)amido-amine. Par "motif acide (poly)carboxylique", on entend un motif portant une ou plusieurs fonctions acides carboxyliques. Ce motif est avantageusement obtenu à partir d'un monomère insaturé portant au moins une, et de préférence deux, fonctions acides carboxyliques, choisi par exemple parmi l'acide maléique, l'acide fumarique, l'acide itaconique, l'acide citraconique, l'anhydride cis-1,2,3,6-tétrahydro-phthalique, l'acide maléique étant préféré. Ces motifs acides carboxyliques peuvent être neutralisés à l'aide de sels de sodium, de potassium ou d'ammonium, de préférence de sels de sodium. Le motif (poly)amido-amine peut être obtenu par réaction de tout ou partie des fonctions acides carboxyliques avec un composé, de préférence un polymère, portant au moins deux fonctions amines primaires ou secondaires, qui peut être choisi notamment parmi : les polyamines telles que la DETA (diéthylène triamine), la TETA (triéthylène tétramine), la TEPA (tétraéthylène pentamine), la dihexylène triamine et la polyéthylèneimine (PEI) ; les polymères siliconés, en particulier les polydiméthylsiloxanes, fonctionnalisés par des groupements aminés ; les chitosans ; les polypeptides et protéines, de préférence la DETA et la PEI.The copolymer used according to the present invention may consist solely of (i) units comprising (and preferably consisting of) an optionally neutralized styrene sulfonic acid unit and (ii) units containing (and preferably consisting of) an acid unit optionally neutralized (poly)carboxylic acid and/or at least one (poly)amido-amine unit. By "(poly)carboxylic acid unit", is meant a unit carrying one or several carboxylic acid functions. This unit is advantageously obtained from an unsaturated monomer carrying at least one, and preferably two, carboxylic acid functions, chosen for example from maleic acid, fumaric acid, itaconic acid, citraconic acid, cis-1,2,3,6-tetrahydro-phthalic anhydride, maleic acid being preferred. These carboxylic acid units can be neutralized using sodium, potassium or ammonium salts, preferably sodium salts. The (poly)amido-amine unit can be obtained by reaction of all or part of the carboxylic acid functions with a compound, preferably a polymer, carrying at least two primary or secondary amine functions, which can be chosen in particular from: polyamines such as as DETA (diethylene triamine), TETA (triethylene tetramine), TEPA (tetraethylene pentamine), dihexylene triamine and polyethyleneimine (PEI); silicone polymers, in particular polydimethylsiloxanes, functionalized with amino groups; chitosans; polypeptides and proteins, preferably DETA and PEI.

On préfère que le pourcentage molaire, dans le copolymère selon l'invention, d'unités renfermant un motif acide styrène sulfonique éventuellement neutralisé soit compris entre 10 et 90%, de préférence entre 25 et 75% et, mieux, entre 50 et 70%.It is preferred that the molar percentage, in the copolymer according to the invention, of units containing an optionally neutralized styrene sulfonic acid unit be between 10 and 90%, preferably between 25 and 75% and, better still, between 50 and 70% .

Ce copolymère peut renfermer au moins une autre unité chimiquement distincte de celles précitées et qui peut par exemple représenter au plus 20% mol et de préférence au plus 10% mol, par rapport au nombre de moles totales d'unités monomères dans ledit copolymère. Cette autre unité peut être choisie notamment parmi les (méth)acrylamides, les esters d'acide (méth)acrylique, l'acétate de vinyle, le styrène et le vinyltoluène.This copolymer may contain at least one other unit chemically distinct from those mentioned above and which may for example represent at most 20 mol% and preferably at most 10 mol%, relative to the number of total moles of monomer units in said copolymer. This other unit can be chosen in particular from (meth)acrylamides, (meth)acrylic acid esters, vinyl acetate, styrene and vinyltoluene.

Le copolymère utilisé selon l'invention répond avantageusement à la formule suivante :

Figure imgb0001
où m/(m+n) = 0,1-0,9 et n/(m+n) = 0,9-0,1, de préférence m/ (m+n) = 0,25-0,75 et n/(m+n) = 0,75-0,25, et plus préférentiellement m/ (m+n) = 0,3-0,5 et n/(m+n) = 0,5-0,7.The copolymer used according to the invention advantageously corresponds to the following formula:
Figure imgb0001
 where m/(m+n) = 0.1-0.9 and n/(m+n) = 0.9-0.1, preferably m/ (m+n) = 0.25-0.75 and n/(m+n)=0.75-0.25, and more preferably m/(m+n)=0.3-0.5 and n/(m+n)=0.5-0, 7.

Selon une forme d'exécution particulièrement préférée de l'invention, tout ou partie des fonctions acides carboxyliques du copolymère sont substituées par des fonctions amido-amines résultant, comme indiqué précédemment, de la réaction de ces fonctions acides carboxyliques avec au moins deux fonctions amines primaires ou secondaires portées par un composé qui est mis à réagir avec les unités renfermant au moins un motif acide (poly)carboxylique du copolymère selon l'invention. Il a en effet été observé que ces copolymères présentaient des propriétés améliorées d'inhibition de la formation de dépôts sulfures. On pense que ces copolymères permettent d'obtenir un effet inhibiteur prolongé, par hydrolyse progressive des fonctions amides, et également plus efficace, dans la mesure où le doublet libre de l'atome d'azote des fonctions amines n'ayant pas participé aux liaisons amides est utile pour complexer les sites de surface des particules de sulfure de zinc et de plomb. Ces copolymères à fonctions amido-amines limitent également les interactions entre les unités acides (poly)carboxyliques et des dépôts de sulfate de baryum ou de carbonate de calcium, par exemple, ce qui peut permettre d'éviter que le copolymère réagisse exclusivement avec ces dépôts qui ont tendance, dans certaines conditions, à se former avant les dépôts de sulfures.According to a particularly preferred embodiment of the invention, all or part of the carboxylic acid functions of the copolymer are substituted by amido-amine functions resulting, as indicated previously, from the reaction of these carboxylic acid functions with at least two amine functions primary or secondary carried by a compound which is reacted with the units containing at least one (poly)carboxylic acid unit of the copolymer according to the invention. It has in fact been observed that these copolymers exhibit improved properties for inhibiting the formation of sulphide deposits. It is believed that these copolymers make it possible to obtain a prolonged inhibitory effect, by progressive hydrolysis of the amide functions, and also more effective, insofar as the free doublet of the nitrogen atom of the amine functions not having participated in the bonds amides is useful for complexing the surface sites of zinc and lead sulfide particles. These copolymers with amido-amine functions also limit the interactions between the (poly)carboxylic acid units and deposits of barium sulphate or calcium carbonate, for example, which can make it possible to prevent the copolymer from reacting exclusively with these deposits which tend, under certain conditions , to form before the sulphide deposits.

Le copolymère utilisé selon l'invention présente en général une masse moléculaire moyenne comprise entre 10 et 50 kDa.The copolymer used according to the invention generally has an average molecular weight of between 10 and 50 kDa.

Ce copolymère peut être obtenu suivant des procédés classiques de polymérisation radicalaire en voie aqueuse ou hydro-alcoolique et à pH acide. Il est également disponible dans le commerce auprès des sociétés ALDRICH ou AKZO NOBEL.This copolymer can be obtained according to conventional processes of radical polymerization in aqueous or aqueous-alcoholic way and at acid pH. It is also commercially available from ALDRICH or AKZO NOBEL.

Du fait de sa bonne tenue thermique, le polymère selon l'invention peut être utilisé en particulier dans des puits pétroliers fonctionnant à haute pression, c'est-à-dire à plus de 10 MPa, par exemple de 20 à 150 MPa, et à haute température, c'est-à-dire de 150 à 250°C, par exemple de 200 à 230°C.Due to its good thermal resistance, the polymer according to the invention can be used in particular in oil wells operating at high pressure, that is to say at more than 10 MPa, for example from 20 to 150 MPa, and at high temperature, that is to say from 150 to 250°C, for example from 200 to 230°C.

Ce polymère peut être injecté dans le puits sous forme d'additif dans un fluide de forage. Ce fluide de forage peut renfermer de 1 à 10 ppm du polymère décrit précédemment.This polymer can be injected into the well as an additive in a drilling fluid. This drilling fluid may contain from 1 to 10 ppm of the polymer described above.

En variante, le polymère décrit précédemment peut être injecté dans le puits en "squeeze", c'est-à-dire suivant un procédé consistant à rincer le puits à l'eau de mer, puis à injecter dans le puits un fluide contenant ce polymère et à introduire à nouveau de l'eau de mer dans le puits pour disperser le polymère dans le réservoir et lui permettre de s'adsorber sur les formations rocheuses souterraines. Lors de ce traitement, les opérations d'extraction de pétrole sont interrompues et, lorsqu'elles seront reprises, le polymère sera libéré progressivement des formations rocheuses pour empêcher ou ralentir la formation des dépôts de sulfures. Dans cette variante, le fluide injecté peut renfermer de l'ordre de 10% en poids du polymère décrit ci-dessus.As a variant, the polymer described above can be injected into the well in "squeeze", that is to say following a process consisting in rinsing the well with sea water, then injecting a fluid containing this polymer into the well and again introducing sea water into the well to disperse the polymer in the reservoir and allow it to adsorb on the underground rock formations. During this treatment, oil extraction operations are interrupted and, when they are resumed, the polymer will be gradually released from the rock formations to prevent or slow the formation of sulphide deposits. In this variant, the injected fluid may contain about 10% by weight of the polymer described above.

Dans tous les cas, le fluide véhiculant le copolymère selon l'invention peut en outre contenir d'autres additifs tels que des inhibiteurs de corrosion, des inhibiteurs de paraffines, des agents tensioactifs ou des agents démulsionnants, des agents dispersants, notamment des dispersants d'asphaltène, des agents moussants ou des agents anti-mousse, des agents biocides, des capteurs d'oxygène, des agents chélatants tels que d'EDTA et le DTPA, et leurs mélanges.In all cases, the fluid carrying the copolymer according to the invention may also contain other additives such as corrosion inhibitors, paraffin inhibitors, surfactants or demulsifying agents, dispersing agents, in particular dispersants of asphaltene, foaming agents or anti-foaming agents, biocidal agents, oxygen scavengers, chelating agents such as EDTA and DTPA, and mixtures thereof.

Selon une forme d'exécution avantageuse de l'invention, ce fluide renferme en outre au moins un polymère porteur de fonctions amines, telles que les polyamines citées précédemment, notamment la DETA ou la PEI, les polymères siliconés porteurs de fonctions amines, et leurs mélanges.According to an advantageous embodiment of the invention, this fluid also contains at least one polymer bearing amine functions, such as the polyamines mentioned above, in particular DETA or PEI, silicone polymers bearing amine functions, and their mixtures.

La présente invention sera mieux comprise à la lumière des exemples non limitatifs suivants, qui sont donnés à titre purement illustratif et n'ont pas pour but de limiter la portée de cette invention qui est définie par les revendications annexées.The present invention will be better understood in the light of the following non-limiting examples, which are given for purely illustrative purposes and are not intended to limit the scope of this invention which is defined by the appended claims.

FIGURESFIGURES

  • La Figure 1 illustre le spectre GPC de l'inhibiteur Fl1 avant et après vieillissement The Figure 1 illustrates the GPC spectrum of the Fl1 inhibitor before and after aging
  • La Figure 2 représente l'évolution de l'intensité de fluorescence à 414 nm avec l'inhibiteur Fl1 à deux températures différentes The Figure 2 represents the evolution of the fluorescence intensity at 414 nm with the Fl1 inhibitor at two different temperatures
  • La Figure 3 représente l'évolution de l'intensité de fluorescence à 414 nm avec l'inhibiteur Fl1 à deux températures différentes The Figure 3 represents the evolution of the fluorescence intensity at 414 nm with the Fl1 inhibitor at two different temperatures
  • La Figure 4 représente l'évolution de l'intensité de fluorescence à 414 nm avec l'inhibiteur Fl1-DETA The Figure 4 represents the evolution of the fluorescence intensity at 414 nm with the Fl1-DETA inhibitor
  • La Figure 5 représente l'évolution de l'intensité de fluorescence à 414 nm avec l'inhibiteur Fl1-DETA à deux températures différentes The Figure 5 represents the evolution of the fluorescence intensity at 414 nm with the Fl1-DETA inhibitor at two different temperatures
  • La Figure 6 illustre le dispositif utilisé pour la mise en œuvre du Tube Blocking Test The Figure 6 illustrates the device used for the implementation of the Tube Blocking Test
EXEMPLESEXAMPLES I/ Préparation de solutions inhibitricesI/ Preparation of inhibitor solutions Exemple 1 : Préparation d'une solution inhibitrice de poly(sodium 4-styrènesulfonate) Example 1 : Preparation of an inhibitor solution of poly(sodium 4-styrenesulfonate)

Le polymère, acheté à Sigma Aldrich ( CAS : 25704-18-1 ; (C8H7NaO3S)n), possède une masse molaire de l'ordre de 100 kDa. Dix grammes de poly(sodium 4-styrenesulfonate) sont pesés dans un flacon de 100 mL. La masse est ensuite ajustée à 100 grammes par ajout d'eau ultra pure. Le pH est alors d'environ 8,7. Le pH est ensuite ajusté à 4.5 par des ajouts d'acide chlorhydrique 6M.The polymer, purchased from Sigma Aldrich ( CAS: 25704-18-1 ; (C 8 H 7 NaO 3 S) n ), has a molar mass of the order of 100 kDa. Ten grams of poly(sodium 4-styrenesulfonate) are weighed into a 100 mL bottle. The mass is then adjusted to 100 grams by adding ultrapure water. pH is then about 8.7. The pH is then adjusted to 4.5 by adding 6M hydrochloric acid.

Exemple 2 : Préparation d'une solution inhibitrice de sel de sodium de poly (acide 4-styrènesulfonique-co-acide maléique) (ou Fl1) Example 2 : Preparation of an inhibitor solution of sodium salt of poly (4-styrenesulfonic acid-co-maleic acid) (or F11)

Le polymère, acheté à Sigma Aldrich ( CAS : 68037-40-1 ; [CH2CH(C6H4SO3R)]x[CH(CO2R)CH(CO2R)]y, R=H or Na), possède une masse molaire de l'ordre de 20 kDa. Le polymère présente un ratio de trois fonctions acide styrène sulfonique pour une fonction acide maléique. Dix grammes de Fil sont pesés dans un flacon de 100 mL. La masse est ensuite ajustée à 100 grammes par ajout d'eau ultra pure. Le pH d'environ 7.5, est ajusté à 4.5 par des ajouts d'acide chlorhydrique 6M.The polymer, purchased from Sigma Aldrich ( CAS: 68037-40-1 ; [CH2CH(C6H4SO3R)] x [CH(CO2R)CH(CO2R)] y , R=H or Na), has a molar mass of around 20 kDa. The polymer has a ratio of three styrene sulfonic acid functions for one maleic acid function. Ten grams of Fil are weighed into a 100 mL bottle. The mass is then adjusted to 100 grams by adding ultrapure water. The pH of around 7.5 is adjusted to 4.5 by adding 6M hydrochloric acid.

Exemple 3 : Préparation d'une solution inhibitrice de sel de sodium de poly (acide 4-styrènesulfonique-co-acide maléique) (ou Fllb) Example 3 : Preparation of an inhibitor solution of sodium salt of poly (4-styrenesulfonic acid-co-maleic acid) (or Fllb)

Le polymère, acheté à Sigma Aldrich ( CAS : 68037-40-1 ; [CH2CH(C6H4SO3R)]x[CH(CO2R)CH(CO2R)]y, R=H or Na), possède une masse molaire de l'ordre de 20 kDa. Le polymère présente un ratio équimolaire de fonctions acide styrène sulfonique et acide maléique. Dix grammes de Fl1b sont pesés dans un flacon de 100 mL. La masse est ensuite ajustée à 100 grammes par ajout d'eau ultra pure. Le pH d'environ 7.5 est ajusté à 4.5 par des ajouts d'acide chlorhydrique 6M.The polymer, purchased from Sigma Aldrich ( CAS: 68037-40-1 ; [CH2CH(C6H4SO3R)] x [CH(CO2R)CH(CO2R)] y , R=H or Na), has a molar mass of around 20 kDa. The polymer has an equimolar ratio of styrene sulfonic acid and maleic acid functions. Ten grams of Fl1b are weighed into a 100 mL bottle. The mass is then adjusted to 100 grams by adding ultrapure water. The pH of about 7.5 is adjusted to 4.5 by adding 6M hydrochloric acid.

Exemple 4 : Préparation d'une solution inhibitrice de Fl1-DETA Example 4 : Preparation of a Fl1-DETA Inhibitor Solution

Dans un flacon de 100 mL, on a fait réagir 10g de Fl1, obtenu suivant l'exemple 2, avec 2g de diethylènetriamine d'une masse molaire de 103.17 g.mol-1 achetée à Sigma Aldrich ( CAS : 111-40-0 ; (NH2CH2CH2) 2NH) . Le pH d'environ 11 est ajusté à 4.5 par ajout d'HCl 6M.In a 100 mL flask, 10 g of Fl1, obtained according to Example 2, was reacted with 2 g of diethylenetriamine with a molar mass of 103.17 g.mol -1 purchased from Sigma Aldrich ( CAS: 111-40-0 ; (NH 2 CH 2 CH 2 ) 2NH). The pH of about 11 is adjusted to 4.5 by adding 6M HCl.

Exemple 5 : Préparation d'une solution inhibitrice de Fl1-PEI Example 5 : Preparation of a Fl1-PEI inhibitor solution

Dans un ballon monocol de 50 mL, 10 g de Fl1 sont placés en présence de 10 mL d'une solution de polyéthylènimine ou PEI ( CAS 9002-98-6 ) à 50% en poids. Le ballon est coiffé d'un réfrigérant et placé sous agitation. 40 mL d'eau ultra pure sont ensuite additionnés. Le tout est chauffé à 80°C pendant 3h, puis 40 mL d'eau ultra pure sont ajoutés et le montage est maintenu en température pendant 24h. Après retour à température ambiante, le contenu du ballon est dispersé dans 100 mL d'eau ultra pure pour donner un produit d'aspect laiteux à 5% en poids de Fl1 et 2,5% de PEI. Le pH est ajusté à 4,5 à l'aide d'HCl 1,2 M.In a 50 mL single-neck flask, 10 g of Fl1 are placed in the presence of 10 mL of a solution of polyethylenimine or PEI ( CAS 9002-98-6 ) to 50% by weight. The flask is capped with a condenser and placed under stirring. 40 mL of ultrapure water are then added. The whole is heated at 80° C. for 3 hours, then 40 mL of ultrapure water are added and the assembly is maintained at temperature for 24 hours. After returning to ambient temperature, the contents of the flask are dispersed in 100 mL of ultrapure water to give a product with a milky appearance containing 5% by weight of F11 and 2.5% of PEI. The pH is adjusted to 4.5 using 1.2 M HCl.

II/ Evaluation du vieillissement thermique des solutions inhibitrices.II/ Evaluation of thermal aging of inhibitor solutions.

Ces tests sont effectués sur une période de cinq jours. De l'azote est préalablement mis à buller dans les échantillons afin d'éliminer l'oxygène. Les tests sont effectués dans des conditions anaérobies sous une température de 200°C et une pression d'azote de l'ordre de 6.89 MPa (1000 psi), appliquées tout au long du vieillissement.These tests are carried out over a period of five days. Nitrogen is bubbled through the samples beforehand in order to eliminate the oxygen. The tests are carried out under anaerobic conditions under a temperature of 200°C and a nitrogen pressure of the order of 6.89 MPa (1000 psi), applied throughout ageing.

Afin de déterminer la stabilité des produits analysés sous de telles conditions, les variations de pression sont étudiées en fonction du temps. Une augmentation de la pression traduit en effet un dégagement gazeux lié à une probable décomposition du produit. Le changement d'aspect des solutions (précipitation, changement de couleur, etc.) peut également renseigner sur la stabilité des produits testés. Une mesure du pH peut être effectuée avant et après vieillissement. Une analyse des produits par GPC avant et après vieillissement peut également mettre en évidence la stabilité des produits.In order to determine the stability of the products analyzed under such conditions, pressure variations are studied as a function of time. An increase in pressure in fact reflects a gas release linked to a probable decomposition of the product. The change in appearance of the solutions (precipitation, color change, etc.) can also provide information on the stability of the products tested. A pH measurement can be performed before and after ageing. An analysis of the products by GPC before and after aging can also highlight the stability of the products.

Exemple 6 : Vieillissement du Fl1 Example 6 : Aging of Fl1

Dans un réacteur sous pression d'azote de 6.89 MPa (~1000 psi) sont placés dans une cellule en verre 70mL de la solution de Fl1 de l'exemple 2 dans laquelle on a préalablement fait buller de l'azote. Après vieillissement à 200°C pendant cinq jours, le Fil subi une augmentation d'une unité de pH environ (de 4.3 à 5.4). Comme illustré à la Figure 1, des analyses par chromatographie en phase gazeuse (GPC) avant et après vieillissement ne montrent pas de changement du produit (pas de déplacement ni d'apparition de pics), qui conserve par ailleurs le même aspect (solution jaune foncée). Le Fl1 est donc thermiquement stable.In a reactor under nitrogen pressure of 6.89 MPa (~1000 psi) are placed in a glass cell 70mL of the F11 solution of Example 2 in which nitrogen has previously been bubbled. After aging at 200°C for five days, the Fil underwent an increase of approximately one pH unit (from 4.3 to 5.4). As shown in Figure 1 , analyzes by gas phase chromatography (GPC) before and after aging show no change in the product (no displacement or appearance of peaks), which moreover retains the same appearance (dark yellow solution). Fl1 is therefore thermally stable.

Exemple 7 : Vieillissement du Fl1-DETA Example 7 : Aging of Fl1-DETA

Dans un réacteur sous pression d'azote de 6.89 MPa (~1000 psi) sont placés dans une cellule en verre, 70mL de la solution de Fl1-DETA de l'exemple 4 dans laquelle on a préalablement fait buller de l'azote. Après vieillissement à 200 °C pendant cinq jours, le Fl1-DETA subi une augmentation de trois unités de pH environ (de 5.56 à 8.25). Des analyses par chromatographie en phase gazeuse (GPC) avant et après vieillissement ne montrent pas de changement du produit (pas de déplacement ni d'apparition de pics) qui conerve par ailleurs le même aspect (solution jaune foncée). Le Fl1-DETA est donc thermiquement stable.In a reactor under nitrogen pressure of 6.89 MPa (~1000 psi) are placed in a glass cell, 70 mL of the solution of F11-DETA of Example 4 in which nitrogen has previously been bubbled. After aging at 200°C for five days, Fl1-DETA experienced an increase in about three pH units (from 5.56 to 8.25). Analyzes by gas phase chromatography (GPC) before and after aging show no change in the product (no displacement or appearance of peaks) which, moreover, retains the same appearance (dark yellow solution). Fl1-DETA is therefore thermally stable.

III/ Evaluation de l'effet inhibiteur par fluorimétrieIII/ Evaluation of the inhibitory effect by fluorimetry

Une solution de soufre est préparée à deux concentrations (100 mg.L-1 et 200mg.L-1) de soufre par dilution de Na2S.9H2O (Aldrich, 98 wt%) dans de l'eau ultra pure. Le contenu de la fiole est versé dans un erlenmeyer muni d'un sérum cap au travers duquel un pH mètre mesure en continu le pH de la solution. Le tout est placé sous agitation mécanique. Des ajouts de solution d'HCl 0.12M sont effectués à l'aide d'une seringue via le sérum cap afin d'atteindre un pH de 5.5. La solution est alors répartie à l'aide d'une seringue dans des flacons scellés de 15 mL munis de sérums caps. Les échantillons sont conservés pendant une durée maximum d'une semaine à 5°C.A sulfur solution is prepared at two concentrations (100 mg.L -1 and 200 mg.L -1 ) of sulfur by dilution of Na 2 S.9H 2 O (Aldrich, 98 wt%) in ultra pure water. The contents of the vial are poured into an Erlenmeyer flask equipped with a serum cap through which a pH meter continuously measures the pH of the solution. The whole is placed under mechanical agitation. Additions of 0.12M HCl solution are made using a syringe via the serum cap in order to reach a pH of 5.5. The solution is then distributed using a syringe into sealed 15 mL bottles fitted with serum caps. Samples are stored for a maximum of one week at 5°C.

Une solution zincique est préparée à 150 mg.L-1 de zinc par dissolution de 157 mg de ZnCl2 (Aldrich, 98wt%) dans une fiole jaugée de 500 mL à l'aide d'une solution saline (25 g.L-1 [Na+] et 5 g.L-1 [Ca2+]). Le pH de la solution est ajusté à 4.5 par ajouts successifs d'une solution d'HCl à 0.12M.A zinc solution is prepared at 150 mg.L -1 of zinc by dissolving 157 mg of ZnCl 2 (Aldrich, 98wt%) in a 500 mL volumetric flask using a saline solution (25 gL -1 [ Na + ] and 5 gL -1 [Ca 2+ ]). The pH of the solution is adjusted to 4.5 by successive additions of a 0.12M HCl solution.

Les inhibiteurs sont préparés à 5% en poids dans l'eau et le pH est ajusté à 4.5 à l'aide d'une solution de HCl à 0.12M et 12M. Les inhibiteurs sont ensuite ajoutés à différentes concentrations (10, 30, 50 et 100 ppm) dans la solution zincique préparée précédemment. Les pH sont contrôlés et réajustés si besoin à l'aide d'HCl à 0.12M ou de NaOH à 0,1M.The inhibitors are prepared at 5% by weight in water and the pH is adjusted to 4.5 using a 0.12M and 12M HCl solution. The inhibitors are then added at different concentrations (10, 30, 50 and 100 ppm) in the zinc solution prepared previously. The pHs are checked and readjusted if necessary using 0.12M HCl or 0.1M NaOH.

Les mesures sont effectuées à l'aide d'un spectrofluorimètre Varian Cary Eclipse. La fluorescence du ZnS est tout d'abord évaluée par analyse d'un échantillon témoin dans lequel du Zinc est mis en présence de soufre sans conditions salines particulières. Les conditions d'analyse standard comprennent λexc = 414 nm et λem = 434 nm. Des variations de la concentration de soufre au cours du temps, liées au dégagement de sulfure d'hydrogène, imposent de changer de capsule toutes les demi-douzaines de mesures, ainsi que d'effectuer des références fréquentes entre les mesures. Les analyses sont effectuées tout d'abord à température ambiante (20°C) puis à 80°C. Elles sont réalisées dans des cuves en PMMA.The measurements are carried out using a Varian Cary Eclipse spectrofluorimeter. The fluorescence of ZnS is first of all evaluated by analysis of a control sample in which Zinc is placed in the presence of sulfur without particular saline conditions. Standard analysis conditions include λexc = 414 nm and λem = 434 nm. Variations in the sulfur concentration over time, linked to the release of hydrogen sulphide, make it necessary to change the capsule every half-dozen measurements, as well as to make frequent references between measurements. The analyzes are carried out first of all at ambient temperature (20°C) then at 80°C. They are made in PMMA tanks.

Trois millilitres de la solution zincique sont mis en présence de 0,5 mL d'une des solutions de soufre préparées et une analyse est effectuée, qui fait office de référence. Par la suite, on met rapidement en présence 3mL de solution contenant l'inhibiteur, à la concentration souhaitée, et le chlorure de zinc (à confirmer), avec 0.5 mL d'une des solutions de soufre, avant de lancer l'analyse. Dans le cas des tests à 80°C, les échantillons sont placés pendant une heure dans une étuve à 80°C. Les analyses sont alors effectuées en utilisant un porte-échantillon thermostaté réglé sur 80°C. Les échantillons sont excités à 414 nm, et on enregistre le spectre de fluorescence entre 425 nm et 450 nm.Three milliliters of the zinc solution are placed in the presence of 0.5 mL of one of the sulfur solutions prepared and an analysis is carried out, which acts as a reference. Subsequently, 3 mL of solution containing the inhibitor, at the desired concentration, and the zinc chloride (to be confirmed), are quickly brought together with 0.5 mL of one of the sulfur solutions, before starting the analysis. In the case of tests at 80°C, the samples are placed for one hour in an oven at 80°C. The analyzes are then carried out using a thermostatically controlled sample holder set at 80°C. The samples are excited at 414 nm, and the fluorescence spectrum is recorded between 425 nm and 450 nm.

Exemple 8 : Suivi de l'effet inhibiteur de ZnS du Fl1 Example 8 : Monitoring of the ZnS inhibitory effect of F11

Cinq millilitres de la solution de Fl1 de l'exemple 2 sont placés dans un flacon de 10 mL auquel sont ajoutés 5 mL d'eau ultra pure. Une solution à 5% en poids de Fl1 est alors obtenue. Le pH de cette solution est ajusté à 4.5 par des ajouts d'HCl 6M. Après quoi, 2, 6 et 10 µL de cette solution sont placés à l'aide d'une micropipette dans des flacons de 10mL. Sont ensuite ajoutés respectivement dans chaque flacon 9998, 9994 et 9990 µL de la solution zincique décrite précédemment pour obtenir trois solutions à 10, 30 et 50 ppm de Fl1. Le pH des solutions est ajusté à 4.5 si besoin par des ajouts d'HCl 0.12M. Les solutions sont ensuite analysées à température ambiante puis à 80°C selon le protocole décrit ci-dessus, avec une solution de soufre à 100 mg.L-1. Les courbes de fluorescence obtenues sont illustrées à la Figure 2. Comme il ressort de cette figure, le Fil ralentit clairement la croissance du ZnS dans ces conditions. L'effet inhibiteur de ce dernier semble exacerbé dans des conditions de température plus élevées.Five milliliters of the F11 solution of Example 2 are placed in a 10 mL bottle to which 5 mL of ultrapure water are added. A 5% by weight solution of Fl1 is then obtained. The pH of this solution is adjusted to 4.5 by adding 6M HCl. After which, 2, 6 and 10 μL of this solution are placed using a micropipette in 10mL bottles. 9998, 9994 and 9990 μL of the zinc solution described above are then added respectively to each flask to obtain three solutions at 10, 30 and 50 ppm of Fl1. The pH of the solutions is adjusted to 4.5 if necessary by adding 0.12M HCl. The solutions are then analyzed at ambient temperature then at 80° C. according to the protocol described above, with a sulfur solution at 100 mg.L −1 . The fluorescence curves obtained are illustrated in Figure 2 . As can be seen from this figure, Fil clearly slows the growth of ZnS under these conditions. The inhibitory effect of the latter seems to be exacerbated under higher temperature conditions.

Exemple 9 : Suivi de l'effet inhibiteur de ZnS du Fl1b Example 9 : Monitoring of the ZnS inhibitory effect of F11b

Cinq millilitres de la solution de Fl1 b de l'exemple 3 sont placés dans un flacon de 10 mL auquel sont ajoutés 5mL d'eau ultra pure. Une solution à 5% en poids de Fl1 est alors obtenue. Le pH de cette solution est ajusté à 4.5 par des ajouts d'HCl 6M. Après quoi, 2, 6 et 10 µl de cette solution sont placés à l'aide d'une micropipette dans des flacons de 10mL. Sont ensuite ajoutés respectivement dans chaque flacon 9998, 9994 et 9990 µl de la solution zincique décrite précédemment pour obtenir trois solutions à 10, 30 et 50 ppm de Fl1 b. Le pH des solutions est ajusté à 4.5 si besoin par des ajouts d'HCl 0.12M. Les solutions sont ensuite analysées à température ambiante puis à 80°C selon le protocole décrit ci-dessus, avec une solution de soufre à 100 mg.L-1. Les courbes de fluorescence obtenues sont illustrées à la Figure 3. Comme il ressort de cette figure, le Fl1b ralenti clairement la croissance du ZnS dans ces conditions. L'effet inhibiteur de ce dernier semble exacerbé dans des conditions de température plus élevées.Five milliliters of the F11b solution of Example 3 are placed in a 10 mL bottle to which 5 mL of ultrapure water are added. A 5% by weight solution of Fl1 is then obtained. The pH of this solution is adjusted to 4.5 by adding 6M HCl. After which, 2, 6 and 10 μl of this solution are placed using a micropipette in 10mL bottles. Are then added respectively in each vial 9998, 9994 and 9990 µl of the zinc solution described previously to obtain three solutions at 10, 30 and 50 ppm of Fl1 b. The pH of the solutions is adjusted to 4.5 if necessary by adding 0.12M HCl. The solutions are then analyzed at ambient temperature then at 80° C. according to the protocol described above, with a sulfur solution at 100 mg.L −1 . The fluorescence curves obtained are illustrated in Figure 3 . As can be seen from this figure, Fl1b clearly slowed the growth of ZnS under these conditions. The inhibitory effect of the latter seems to be exacerbated under higher temperature conditions.

Exemple 10 : Suivi de l'effet inhibiteur de ZnS du Fl1-DETA Example 10 : Monitoring the ZnS Inhibitory Effect of Fl1-DETA

Cinq millilitres de la solution de Fl1-DETA de l'exemple 4 sont placés dans un flacon de 10 mL auquel sont ajoutés 5mL d'eau ultra pure. Une solution à 5% en poids de Fl1-DETA (10:2) est alors obtenue. Le pH de cette solution est ajusté à 4.5 par des ajouts d'HCl 6M. Après quoi, 1, 4 et 10 µL de cette solution sont placés à l'aide d'une micropipette dans des flacons de 10mL. Sont ensuite ajoutés respectivement dans chaque flacon 9999, 9996 et 9990 µL de la solution zincique décrite précédemment pour obtenir trois solutions à 5, 20 et 50 ppm de Fl1-DETA. Le pH des solutions est ajusté à 4.5 si besoin par des ajouts d'HCl 0.12M. Les solutions sont ensuite analysées à température ambiante selon le protocole décrit ci-dessus 11 avec une solution de soufre à 100 mg.L-1. Les courbes de fluorescence obtenues sont illustrées à la Figure 4. Comme il ressort de cette figure, une diminution de la croissance du sulfure de zinc est observée avec l'augmentation de la concentration en Fl1-DETA (10:2). Le Fl1-DETA inhibe clairement la formation du ZnS.Five milliliters of the F11-DETA solution of Example 4 are placed in a 10 mL bottle to which 5 mL of ultrapure water are added. A 5% by weight solution of F11-DETA (10:2) is then obtained. The pH of this solution is adjusted to 4.5 by adding 6M HCl. After which, 1, 4 and 10 μL of this solution are placed using a micropipette in 10mL bottles. 9999, 9996 and 9990 μL of the zinc solution described above are then added respectively to each flask to obtain three solutions at 5, 20 and 50 ppm of Fl1-DETA. The pH of the solutions is adjusted to 4.5 if necessary by adding 0.12M HCl. The solutions are then analyzed at room temperature according to the protocol described above 11 with a sulfur solution at 100 mg.L -1 . The fluorescence curves obtained are illustrated in Figure 4 . As can be seen from this figure, a decrease in zinc sulfide growth is observed with increasing Fl1-DETA concentration (10:2). Fl1-DETA clearly inhibits the formation of ZnS.

Exemple 11 : Suivi de l'effet inhibiteur de ZnS du Fl1-PEI. Example 11 : Monitoring of the ZnS inhibitory effect of F11-PEI.

Cinq millilitres de la solution de Fl1-PEI sont placés dans un flacon de 10 mL auquel sont ajoutés 5mL d'eau ultra pure. Une solution à 5 en poids de Fl1-PEI (10:5) est alors obtenue. Le pH de cette solution est ajusté à 4.5 par des ajouts d'HCl 6M. Après quoi, 2, 6 et 10 µl de cette solution sont placés à l'aide d'une micropipette dans des flacons de 10mL. Sont ensuite ajoutés respectivement dans chaque flacon 9998, 9994 et 9990 µL de la solution zincique décrite précédemment pour obtenir trois solutions à 5, 30 et 50 ppm de Fl1-PEI. Le pH des solutions est ajusté à 4.5 si besoin par des ajouts d'HCl 0.12M. Les solutions sont ensuite analysées à température ambiante selon le protocole décrit ci-dessus avec une solution de soufre à 100 mg.L-1. Les courbes de fluorescence obtenue sont illustrées à la Figure 5. Comme il ressort de cette figure, le Fl1-PEI a un effet inhibiteur sur le sulfure de zinc à température ambiante. Ce pouvoir inhibiteur est exacerbé dans des conditions de température plus élevées.Five milliliters of the Fl1-PEI solution are placed in a 10 mL bottle to which 5 mL of ultrapure water are added. A 5 w/w solution of F11-PEI (10:5) is then obtained. The pH of this solution is adjusted to 4.5 by adding 6M HCl. After which, 2, 6 and 10 μl of this solution are placed using a micropipette in 10mL bottles. 9998, 9994 and 9990 μL of the zinc solution described above are then added respectively to each flask to obtain three solutions at 5, 30 and 50 ppm of Fl1-PEI. The pH of the solutions is adjusted to 4.5 if necessary by adding 0.12M HCl. The solutions are then analyzed at room temperature according to the protocol described above with a sulfur solution at 100 mg.L -1 . The fluorescence curves obtained are illustrated in Figure 5 . As can be seen from this figure, Fl1-PEI has an inhibitory effect on zinc sulfide at room temperature. This inhibitory power is exacerbated under higher temperature conditions.

IV/ Evaluation de l'effet inhibiteur par le Tube Blocking Test. IV/ Evaluation of the inhibitory effect by the Tube Blocking Test.

Deux solutions salines contenant des cations métalliques (A) et du soufre (B) sont mélangées puis passent dans un tube où un dépôt se forme. Le tube est muni d'un filtre. Lorsque le dépôt est formé dans les tubes, leur surface intérieure diminue et le filtre se bouche, ce qui conduit à une augmentation de la pression différentielle. Les inhibiteurs sont mélangés dans la solution A et sont testés entre 5 et 30 ppm. Une analyse du filtre par SEM puis par EDX permet d'obtenir des informations précises sur la quantité et la nature des dépôts formés.Two saline solutions containing metal cations (A) and sulfur (B) are mixed and then passed through a tube where a deposit forms. The tube is equipped with a filter. When the deposit is formed in the tubes, their surface interior decreases and the filter clogs, which leads to an increase in the differential pressure. The inhibitors are mixed in solution A and are tested between 5 and 30 ppm. An analysis of the filter by SEM then by EDX makes it possible to obtain precise information on the quantity and nature of the deposits formed.

Le dispositif utilisé est représenté à la Figure 6 annexée.The device used is shown in Figure 6 annexed.

Les tests sont effectués avec une solution B qui est toujours la même, mais avec des solutions A pouvant contenir des éléments de différentes nature, résumées dans le Tableau 1. Tableau 1 Conditions expérimentales du Tube Blocking Test Ion Solution A1 (mg/l) Solution A2 (mg/l) Solution A3 (mg/l) Solution A4 (mg/l) Solution A5 (mg/l) Solution B (mg/l) Na 63310 63310 29505 63310 63310 117576 Ca 37318 37318 7223 37318 37318 0 Mg 2174 2174 511 2174 2174 0 K 21198 21198 0 21198 21198 0 Ba 4946 4946 0 4946 4946 0 Sr 4480 4480 0 4480 4480 0 Fe 900 0 0 0 450 0 Pb 100 0 0 50 0 0 Zn 300 300 200 0 300 0 s 0 0 0 0 0 10 The tests are carried out with a solution B which is always the same, but with solutions A which may contain elements of different kinds, summarized in Table 1. <b>Table 1</b> Tube Blocking Test experimental conditions Ion Solution A1 (mg/l) Solution A2 (mg/l) Solution A3 (mg/l) Solution A4 (mg/l) Solution A5 (mg/l) Solution B (mg/l) N / A 63310 63310 29505 63310 63310 117576 That 37318 37318 7223 37318 37318 0 mg 2174 2174 511 2174 2174 0 K 21198 21198 0 21198 21198 0 Ba 4946 4946 0 4946 4946 0 sr 4480 4480 0 4480 4480 0 Fe 900 0 0 0 450 0 bp 100 0 0 50 0 0 Zn 300 300 200 0 300 0 s 0 0 0 0 0 10

Exemple 12 : Suivi de l'effet inhibiteur de ZnS du poly(sodium 4-styrènesulfonate) (PSS). Example 12 : Monitoring of the ZnS inhibitory effect of poly(sodium 4-styrenesulfonate) (PSS).

Afin d'effectuer ces tests, les solutions contenant le PSS utilisées sont à base de la solution A3 du Tableau 1, à laquelle sont ajoutées des quantités de la solution de PSS de l'exemple 1. Les solutions alors obtenues sont à 30, 50 et 100 ppm de PSS. Elles sont o-injectées avec la solution B du Tableau 1, via un tube en alliage (Ni72Cr16Fr8) de 1 mm de diamètre extérieur et de 0.8 mm de diamètre intérieur. Les deux solutions passent ensuite au travers d'un filtre de 7 µm. Les solutions sont injectées avec un débit de 10 mL/min. Une mesure différentielle de la pression est effectuée entre l'entrée et la sortie du filtre. Les tests sont effectués à 125°C et sous une pression de 45 bar. Les résultats obtenus sont rassemblés dans le Tableau 2 ci-dessous. Tableau 2 Résultats du Tube Blocking Test pour le PSS Concentration
(mg/L) ΔP (psi) Dépôts observés Filtre N/A Pas de dépôt (Fe, Cr, Ni du filtre) 0 3,4 Beaucoup de ZnS 30 3,2 Beaucoup de ZnS
(comparable au blanc) 50 2,9 Beaucoup de ZnS
(comparable au blanc) 100 3,5 Beaucoup de ZnS
(comparable au blanc) In order to carry out these tests, the solutions containing the PSS used are based on solution A3 of Table 1, to which are added quantities of the PSS solution of example 1. The solutions then obtained are at 30, 50 and 100 ppm PSS. They are o-injected with solution B from Table 1, via an alloy tube (Ni 72 Cr 16 Fr 8 ) 1 mm outside diameter and 0.8 mm inside diameter. The two solutions then pass through a 7 µm filter. The solutions are injected with a flow rate of 10 mL/min. A differential pressure measurement is made between the inlet and the outlet of the filter. The tests are carried out at 125°C and under a pressure of 45 bar. The results obtained are collated in Table 2 below. <b>Table 2</b> Tube Blocking Test Results for PSS Concentration
(mg/L) ΔP (psi) Observed deposits Filtered N / A No deposit (Fe, Cr, Ni from the filter) 0 3.4 Lots of ZnS 30 3.2 Lots of ZnS
(comparable to white) 50 2.9 Lots of ZnS
(comparable to white) 100 3.5 Lots of ZnS
(comparable to white)

Ces résultats montrent que le PSS ne présente pas d'effet inhibiteur de la formation de dépôts de ZnS.These results show that the PSS does not exhibit any inhibitory effect on the formation of ZnS deposits.

Exemple 13 : Suivi de l'effet inhibiteur de ZnS du Fl1 Example 13 : Monitoring of the ZnS inhibitory effect of F11

Afin d'effectuer ces tests, les solutions contenant le Fl1 utilisées sont à base de la solution A2 du Tableau 1, à laquelle sont ajoutées des quantités de la solution de Fl1 de l'exemple 2. Les solutions obtenues sont à 5, 10, 30 et 100 ppm. Elles sont co-injectées avec la solution B du Tableau 1, via un tube en alliage (Ni72Cr16Fr8) de 1 mm de diamètre extérieur et de 0.8 mm de diamètre intérieur. Les deux solutions passent ensuite au travers d'un filtre de 7 µm. Les solutions sont injectées avec un débit de 10 mL/min. Une mesure différentielle de la pression est effectuée entre l'entrée et la sortie du filtre. Les tests sont effectués à 125°C et sous une pression de 45 bar. Les résultats sont rassemblés dans le Tableau 3 ci-dessous. Tableau 3 Résultats du Tube Blocking Test pour le Fl1 Concentration (mg/l) ΔP (psi) Dépôts observés Filtre N/A Pas de dépôt (Fe, Cr, Ni du Filtre) 0 3,3 Recouvert partiellement de ZnS 5 1,2 Moins de ZnS que dans le blanc 10 1 Traces de ZnS 30 0 Traces de ZnS 100 0 Traces de ZnS In order to carry out these tests, the solutions containing the Fl1 used are based on the solution A2 of Table 1, to which are added quantities of the solution of Fl1 of example 2. The solutions obtained are at 5, 10, 30 and 100 ppm. They are co-injected with solution B of Table 1, via an alloy tube (Ni 72 Cr 16 Fr 8 ) with an outside diameter of 1 mm and an inside diameter of 0.8 mm. The two solutions then pass through a 7 µm filter. The solutions are injected with a flow rate of 10mL/min. A differential pressure measurement is made between the inlet and the outlet of the filter. The tests are carried out at 125°C and under a pressure of 45 bar. The results are collated in Table 3 below. <b>Table 3</b> Fl1 Tube Blocking Test Results Concentration (mg/l) ΔP (psi) Observed deposits Filtered N / A No deposit (Fe, Cr, Ni from the Filter) 0 3.3 Partially coated with ZnS 5 1.2 Less ZnS than in white 10 1 Traces of ZnS 30 0 Traces of ZnS 100 0 Traces of ZnS

Dans ces conditions, le Fl1 est actif dès 5 ppm. En effet, dès cette concentration, le Fl1 ralentit la croissance du ZnS.Under these conditions, Fl1 is active from 5 ppm. Indeed, from this concentration, Fl1 slows the growth of ZnS.

Exemple 14 : Suivi de l'effet inhibiteur de ZnS du Fl1-DETA Example 14 : Monitoring the ZnS Inhibitory Effect of F11-DETA

Afin d'effectuer ces tests, les solutions contenant le Fl1-DETA utilisées sont à base de la solution A2 du Tableau 1, à laquelle sont ajoutées des quantités données de la solution de Fl1-DETA de l'exemple 4. Les solutions obtenues sont à 1, 3, 5, 10 et 30 ppm de Fl1-DETA. Elles sont co-injectées avec la solution B du Tableau 1, via un tube en alliage (Ni72Cr16Fr8) de 1 mm de diamètre extérieur et de 0.8 mm de diamètre intérieur. Les deux solutions passent ensuite au travers d'un filtre de 7 µm. Les solutions sont injectées avec un débit de 10 mL/min. Une mesure différentielle de la pression est effectuée entre l'entrée et la sortie du filtre. Les tests sont effectués à 125°C et sous une pression de 45 bar. Les résultats obtenus sont rassemblés dans le Tableau 4 ci-dessous. Tableau 4 Résultats du Tube Blocking Test pour le Fl1-DETA Concentration (mg/l) AP (psi) Dépôts observés Filtre N/A Pas de dépôt (Fe, Cr, Ni du Filtre) 0 3,2 Recouvert partiellement de ZnS 1 2,7 Moins de ZnS que dans le blanc 3 0 Traces de ZnS 5 0 Traces de ZnS 10 0 Traces de ZnS 30 0 Traces de ZnS In order to carry out these tests, the solutions containing Fl1-DETA used are based on solution A2 of Table 1, to which are added given quantities of the solution of Fl1-DETA of example 4. The solutions obtained are at 1, 3, 5, 10 and 30 ppm of Fl1-DETA. They are co-injected with solution B of Table 1, via an alloy tube (Ni 72 Cr 16 Fr 8 ) with an outside diameter of 1 mm and an inside diameter of 0.8 mm. The two solutions then pass through a 7 µm filter. The solutions are injected with a flow rate of 10 mL/min. A differential pressure measurement is made between the inlet and the outlet of the filter. The tests are carried out at 125°C and under a pressure of 45 bar. The results obtained are collated in Table 4 below. <b>Table 4</b> Fl1-DETA Tube Blocking Test Results Concentration (mg/l) PA (psi) Observed deposits Filtered N / A No deposit (Fe, Cr, Ni from the Filter) 0 3.2 Partially coated with ZnS 1 2.7 Less ZnS than in white 3 0 Traces of ZnS 5 0 Traces of ZnS 10 0 Traces of ZnS 30 0 Traces of ZnS

Dans ces conditions, le Fl1-DETA est actif dès 3 ppm. En effet, dès cette concentration, aucune augmentation de pression n'est observée, ce qui traduit l'absence de formation de dépôt de ZnS.Under these conditions, Fl1-DETA is active from 3 ppm. Indeed, from this concentration, no increase in pressure is observed, which reflects the absence of formation of ZnS deposit.

Claims (9)

  1. Use of a copolymer containing a unit comprising (i) an optionally neutralised styrene sulphonic acid unit and (ii) a unit containing an optionally neutralised (poly)carboxylic acid unit and/or a (poly)amido-amine unit, to inhibit or slow the formation of sulphide deposits, in particular of lead, iron and/or zinc sulphides, during the extraction of gas or oil.
  2. Use according to claim 1, characterised in that the (poly)carboxylic acid unit is obtained using an unsaturated monomer bearing at least one, and more preferably two, carboxylic acid functions.
  3. Use according to claim 2, characterised in that the monomer bearing carboxylic acid functions is chosen from maleic acid, fumaric acid, itaconic acid, citraconic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, more preferably maleic acid.
  4. Use according to one of claims 2 and 3, characterised in that the (poly)amido-amine unit is obtained by reacting all or a portion of the carboxylic acid functions with a compound, more preferably a polymer, bearing at least two primary or secondary amine functions, chosen from among: polyamines such as DETA (diethylene triamine), TETA (triethylene tetramine), TEPA (tetraethylene pentamine), dihexylene triamine and polyethyleneimine (PEI); silicone polymers, in particular polydimethylsiloxanes, functionalised by amine groups; chitosans; polypeptides and proteins, more preferably DETA and PEI.
  5. Use according to any of claims 1 to 4, characterised in that the molar percentage, in the copolymer, of units containing an optionally neutralised styrene sulphonic acid unit is between 10 and 90%, more preferably between 25 and 75% and, better, between 50 and 70%.
  6. Use according to any of claims 1 to 5, characterised in that the copolymer is solely constituted of units comprising, and more preferably constituted of, an optionally neutralised styrene sulphonic acid unit and units containing, and more preferably constituted of, an optionally neutralised (poly)carboxylic acid unit or a (poly)amido-amine unit.
  7. Use according to any of claims 1 to 6, characterised in that the copolymer has an average molecular mass between 10 and 50 kDa.
  8. Method for inhibiting or slowing the formation of sulphide deposits, in particular of lead, iron and/or zinc sulphides, during the extraction of gas or oil, comprising the injection, into a wellbore, a subterranean formation or a gas or oil well, of a fluid containing a copolymer containing (i) a unit comprising an optionally neutralised styrene sulphonic acid unit and (ii) a unit containing at least one optionally neutralised (poly)carboxylic acid unit and/or a (poly)amide unit.
  9. Method according to claim 8, characterised in that the fluid is injected into an oil well operating at more than 10 MPa, for example from 20 to 150 MPa, and at 150 to 250°C, for example from 200 to 230°C.
EP14830835.6A 2013-12-20 2014-12-19 Use of a copolymer made from styrene sulphonic acid to inhibit or slow the formation of sulphide deposits Active EP3083874B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1363289A FR3015512B1 (en) 2013-12-20 2013-12-20 USE OF A STYRENE SULFONIC ACID COPOLYMER TO INHIBIT OR SLOW THE FORMATION OF SULPHIDE DEPOSITS
PCT/FR2014/053442 WO2015092311A1 (en) 2013-12-20 2014-12-19 Use of a copolymer made from styrene sulphonic acid to inhibit or slow the formation of sulphide deposits

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EP3083874A1 EP3083874A1 (en) 2016-10-26
EP3083874B1 true EP3083874B1 (en) 2022-11-02

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US (1) US10106722B2 (en)
EP (1) EP3083874B1 (en)
AR (1) AR098821A1 (en)
FR (1) FR3015512B1 (en)
MY (1) MY177401A (en)
WO (1) WO2015092311A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3064364A1 (en) 2017-03-27 2018-09-28 S.P.C.M. Sa METHOD OF DETERMINING CATIONIC POLYMERS
US11208589B2 (en) * 2019-07-22 2021-12-28 Halliburton Energy Services, Inc. Controlling metal sulfide scale in drilling operations

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171459A (en) 1991-04-30 1992-12-15 Nalco Chemical Company Scale deposition inhibitor
FR2803304B1 (en) 1999-12-29 2006-03-24 Ceca Sa INORGANIC DEPOSIT INHIBITORS, ESPECIALLY IN OIL WELLS
US7159655B2 (en) * 2003-09-25 2007-01-09 Bj Services Company Method for inhibiting or controlling inorganic scale formations
US7398824B1 (en) 2003-09-25 2008-07-15 Bj Services Company Method for inhibiting or controlling inorganic scale formations with copolymers of acrylamide and quaternary ammonium salts
GB2448442B (en) 2004-12-15 2009-07-22 Bj Services Co Well treating compositions for slow release of treatment agents and methods of using the same
EP1886976A1 (en) * 2006-08-09 2008-02-13 Thermphos Trading GmbH Method of scale inhibition
GB0711342D0 (en) * 2007-06-12 2007-07-25 Champion Technologies Ltd Well treatment
US8703655B2 (en) * 2007-06-15 2014-04-22 Baker Hughes Incorporated Dispersing sulfide scales in oil and gas production systems
CA2758686A1 (en) * 2011-11-21 2013-05-21 Kroff Chemical Company Fluid treatment systems, compositions and methods for metal ion stabilization in aqueous solutions

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MY177401A (en) 2020-09-14
AR098821A1 (en) 2016-06-15
FR3015512B1 (en) 2017-01-20
WO2015092311A1 (en) 2015-06-25
US20160333251A1 (en) 2016-11-17
FR3015512A1 (en) 2015-06-26
US10106722B2 (en) 2018-10-23
EP3083874A1 (en) 2016-10-26

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